US4287856A - Engines - Google Patents

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Publication number
US4287856A
US4287856A US06/035,826 US3582679A US4287856A US 4287856 A US4287856 A US 4287856A US 3582679 A US3582679 A US 3582679A US 4287856 A US4287856 A US 4287856A
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United States
Prior art keywords
base metal
monolith
engine according
engine
catalytic
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Expired - Lifetime
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US06/035,826
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English (en)
Inventor
Bernard E. Enga
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Johnson Matthey PLC
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Johnson Matthey PLC
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K3/00—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein
    • F01K3/18—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein having heaters
    • F01K3/188—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein having heaters using heat from a specified chemical reaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B51/00—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines
    • F02B51/02—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines involving catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
    • F02G1/00—Hot gas positive-displacement engine plants
    • F02G1/04—Hot gas positive-displacement engine plants of closed-cycle type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
    • F02G2244/00—Machines having two pistons
    • F02G2244/50—Double acting piston machines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
    • F02G2254/00—Heat inputs
    • F02G2254/10—Heat inputs by burners
    • F02G2254/11—Catalytic burners
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
    • F02G2258/00—Materials used
    • F02G2258/10—Materials used ceramic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • This invention relates to Rankine cycle engines and to improved methods of operation whereby catalytic oxidation of a major proportion of the fuel takes place in the boiler section of the engine.
  • the Carnot cycle is the most efficient heat engine which for a wet vapour consists of four stages. Heat is supplied to the working fluid at constant temperature and pressure followed by isentropic expansion of the vapour. In the third stage heat is rejected isothermally and finally the fluid is isenthropically compressed. This theoretical cycle cannot be followed in practise and the modified cycle is called the Rankine cycle which is less efficient.
  • the basic machinery for this type of engine comprises a boiler, an expander (means for allowing the working fluid to expand), a condenser and a feed pump.
  • An object of the present invention is to produce a Rankine cycle engine in which the boiler unit comprises a catalytic combustor, such that the engine may be used in conditions where there are limits on noise, pollutants, in exhaust gases and flamable substances.
  • the boiler unit of a Rankine cycle engine includes a catalytic combustor having a thermally stable and oxidation resistant monolith containing a multiplicity of flow paths and channels constituting or supporting a catalyst for the catalytic combustion of the combustible gases and injected fuel.
  • the boiler unit of the Rankine cycle engine comprises:
  • a catalytic combustor section comprising a temperature stable oxidation resistant monolith, the monolith providing catalytic channels for contact with and passage of the gases combined with injected fuel at stage (c) such that catalytic combustion of the uncombusted fuel takes place but in which a pressure drop of 10% or less is produced, and
  • the temperature of the air is between 0° C. and 600° C. and at a pressure within the range 1 atmosphere to 20 atmospheres.
  • the pilot burner burns up to approximately 5% by weight of the total fuel consumption of the engine at fuel power.
  • the proportion of the fuel utilised by the pilot burner during normal running may range from 0.16% by weight to 662/3% by weight.
  • the fuel injection for the pilot burner (b) is able to control the quantity of fuel and is adjusted primarily to give a temperature within a specific preferred range in the combustion section (d).
  • a typical preferred temperature range in the combustion section is 200° C. to 500° C.
  • the remainder of the fuel is injected into the gaseous stream, in section (c), by one or more fuel injectors, the number of which and their configuration will be dependent on the condition of operation of the engine.
  • the monolith in section (d) is metallic and is formed from one or more metals selected from the group comprising Ru, Rh, Pd, Ir and Pt.
  • metals selected from the group comprising Ru, Rh, Pd, Ir and Pt.
  • base metals may be used or base metal alloys which also contain a platinum group metal component may be used.
  • the walls of the metallic monolith preferably have a thickness within the range 2-4 thousandths of one inch.
  • the preferred characteristics of the metallic monolith having catalyst deposited thereon are (i) that it presents low resistance to the passage of gases by virtue of its possession of a high ratio of open area to blocked area and (ii) that it has a high surface to volume ratio.
  • a typical 200 cells per square inch ceramic monolith has walls 0.008-0.011 inches thick, a 71% open area and a 15% pressure drop.
  • a typical 400 cells per square inch metallic monolith of the present invention has walls 0.002 inches thick, a 91-92% open area and a 4% pressure drop.
  • a 200 cell per square inch metallic monolith has a 95% open area and a pressure drop of 4% or less.
  • Suitable platinum group metals for use in fabrication of the metallic monolith are platinum, 10% rhodium-platinum and dispersion strengthened platinum group metals and alloys as described in British Patent Nos. 1,280,815 and 1,340,076 and U.S. Pat. Nos. 3,689,987, 3,696,502 and 3,709,667.
  • Base metals which may be used are those capable of withstanding rigorous oxidising conditions.
  • Examples of such base metal alloys are nickel and chromium alloys having an aggregate Ni plus Cr content greater than 20% by weight and alloys of iron including at least one of the elements chromium (3-40)wt.%, aluminium (1-10)wt.%, cobalt (0-5)wt.%, nickel (0.-72)wt.% and carbon (0-0.5)wt.%.
  • Such substrates are described in German OLS No. 2450664.
  • the latter alloys may contain 0.5-12 wt.% Al, 0.1-3.0 wt.% Y, 0-20 wt.% Cr and balance Fe. These are described in U.S. Pat. No. 3,298,826.
  • Another range of Fe-Cr-Al-Y alloys contain 0.5-4 wt.% Al, 0.5-3.0 wt.% Y, 20.0-95.0 wt.% Cr and balance Fe and these are described in U.S. Pat. No. 3,027,252.
  • Base metal alloys which also contain a platinum group metal component are useful as a catalytic metallic monolith in very fierce oxidising conditions.
  • Such alloys are described in German DOS No. 2530245 and contain at least 40 wt.% Ni or at least 40 wt.% Co, a trace to 30 wt.% Cr and a trace to 15 wt.% of one or more of the metals Pt, Pd, Rh, Ir, Os and Ru.
  • the alloys may also contain from a trace to the percentage specified or any one or more of the following elements:
  • the metallic substrate is composed either substantially or solely or platinum group metal it may be in the form of an interwoven wire gauze or mesh or corrugated sheet or foil.
  • the metallic substrate is composed substantially of base metal it is preferably in the form of corrugated sheet or foil.
  • base metal monoliths are also described in German OLS 2450664 and they may be used in the combustor according to the present invention. Such base metal monoliths may have deposited thereon a first layer comprising an oxygen containing coating and a second and catalytic layer.
  • the oxygen containing coating is usually present as an oxide selected from the group consisting of alumina, silica, titania, zirconia, hafnia, thoria, beryllia, magnesia, calcium oxide, strontium oxide, barium oxide, chromia, boria, scandium oxide, yttrium oxide and oxides of the lanthanides.
  • the oxygen in the first layer is present as an oxygen containing anion selected from the group consisting of chromate, phosphate, silicate and nitrate.
  • the second catalytic layer may, for example, comprise a metal selected from the groups consisting of Ru, Rh, Pd, Ir, Pt, Au, Ag, an alloy containing at least one of the said metals and alloys containing at least one of the said metals and a base metal.
  • the first and second layers may be deposited or otherwise applied to the monolith as described in German OLS No. 2450664.
  • a catalyst comprising a metallic substrate having deposited thereon a surface coating consisting of one or more intermetallic compounds of the general formula A x B y where A is selected from the group consisting of Al, Sc, Y, the lanthanides, Ti, Zr, Hf, V, Nb and Ta and x and y are integral and may have values of 1 or more.
  • the surface coating of intermetallic compound is, preferably, in the form of a thin film ranging in thickness from 2 to 15 microns.
  • the intermetallic compound When the intermetallic compound is deposited in the form of a coating not more than 15 microns thick upon the surface of a metallic substrate, excessive brittleness is absent and the coated substrate may be handled normally.
  • a number of different techniques may be employed to produce a coating in the form of a thin film of intermetallic compound upon the surface of the metal metallic monolith.
  • aluminium may be deposited onto the surface of rhodium-platinum gauzes by a pack-aluminising process. In this process the gauzes are packed into a heat-resistant container in an appropriate mixture of chemicals such that aluminium is transferred via the vapour phase to the gauze surface.
  • the aluminising temperature typically 800°-900° C., interaction between the platinum and aluminium occurs to give the required intermetallic compound.
  • chemical vapour deposition from ZrCl 4 can be used to form a layer of Pt 3 Zr, or electrodeposition may be used either from aqueous or fused salt electrolysis to give the requisite compound.
  • the objective is to form a layer of a firmly adherent, intermetallic compound on the wires of the gauze pack or other substrate.
  • the metals forming the intermetallic compound are prepared as an appropriate solution in water or an organic solvent.
  • the compound is caused to deposit upon the metallic substrate or gauze by the addition of a reducing agent.
  • the metallic substrate is placed in the solution whilst the precipitation is taking place and becomes coated with a uniform, microcrystalline layer of the intermetallic compound.
  • the catalyst is preferably a metal selected from the group consisting of Ru, Rd, Pd, Ir, Pt and alloys of the said metals with each other and with one or more base metals such that at least 10% by weight of the said catalyst is PGM.
  • an intermediate washcoat layer may be applied comprising a high surface area refractory metal oxide.
  • the working fluid may be air, water, or organic fluid or a liquid metal.
  • Water is the most frequently used working fluid due to its availability and cheapness but there are a number of disadvantages which can be overcome if an organic fluid or a liquid metal is used.
  • Toluene and hexafluorbenzene are recognized working fluids.
  • the choice of fluid will depend on factors such as the size of the engine and the cost. Modifications have to be made to the engine when using either a liquid metal or an organic fluid.
  • a turbine is used as the expander, the turbine, generator and the feed pump may be positioned on the same shaft.
  • a regenerator is included to transfer the heat of desuperheating to the boiler feed heating.
  • the operation of the boiler unit combustor is as follows: a fan, 20, or similar apparatus such as a compressor provides the inlet of air which is heated by a pilot burner, 22.
  • the supply of fuel to the pilot burner is adjusted for an optimum air temperature over the catalyst supported by the monolith.
  • the remainder of the fuel is injected by fuel injectors 24 into the flow of hot air prior to the monolith, 26. Catalytic combustion of the fuel takes place.
  • the hot exhaust gases are used to heat the working fluid of the Rankine cycle engine.
  • the fuel system and air supply may be driven by any convenient means which is best suited to the environment in which the engine is being operated. For example if the invention was to be used in mines electrical drive motors would be used that were Buxton-certified flame-proof.
  • the expander unit can be a positive displacement engine or a turbine. The choice will be governed by the application for which the Rankine cycle engine will be used.
  • the catalyst was supported on a monolith made from an Fe-Cr-Al-Y alloy as previously described in the specification.
  • the monolith had a cell density of 400 cells per square inch, a diameter of three inches and a length of three inches.
  • the catalyst used was platinum having a loading of 150 grams per cubic foot and, prior to applying the catalyst, the monolith was precoated with a washcoat layer comprising aluminium and barium.
  • the engine was supplied with inlet air at a rate of 42 cubic feet per second which was heated by the pilot burner 22 to a temperature of 38° C.
  • the remainder of the fuel was injected into the gas stream at a position upstream of the catalyst.
  • the exhaust gases leaving the catalyst had a temperature of 625° C. and the wire fed to the boiler where steam was raised.
  • the exhaust gases leaving the boiler had a temperature of 80° C. and a portion of the steam was used to power a double-acting steam piston engine rated at 3 BHP.
  • the level of pollutants present in the exhaust gas is given below for a stable combustion run time of 380 hours and a catalyst light-off temperature of 200° C.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)
US06/035,826 1978-05-08 1979-05-04 Engines Expired - Lifetime US4287856A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB18240/78 1978-05-08
GB1824078 1978-05-08

Publications (1)

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US4287856A true US4287856A (en) 1981-09-08

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US06/035,826 Expired - Lifetime US4287856A (en) 1978-05-08 1979-05-04 Engines

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US (1) US4287856A (sv)
JP (2) JPS5514991A (sv)
CA (1) CA1146362A (sv)
DE (1) DE2918515A1 (sv)
FR (1) FR2425539A1 (sv)
SE (1) SE7904004L (sv)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4966001A (en) * 1987-10-23 1990-10-30 General Electric Company Multiple venturi tube gas fuel injector for catalytic combustor
US5248251A (en) * 1990-11-26 1993-09-28 Catalytica, Inc. Graded palladium-containing partial combustion catalyst and a process for using it
US5250489A (en) * 1990-11-26 1993-10-05 Catalytica, Inc. Catalyst structure having integral heat exchange
US5258349A (en) * 1990-11-26 1993-11-02 Catalytica, Inc. Graded palladium-containing partial combustion catalyst
US5259754A (en) * 1990-11-26 1993-11-09 Catalytica, Inc. Partial combustion catalyst of palladium on a zirconia support and a process for using it
US5511972A (en) * 1990-11-26 1996-04-30 Catalytica, Inc. Catalyst structure for use in a partial combustion process
US20070045101A1 (en) * 2005-07-06 2007-03-01 Rochester Institute Of Technology Self-regenerating particulate trap systems for emissions and methods thereof
US20070044478A1 (en) * 2005-08-29 2007-03-01 Kashmerick Gerald E Combustion engine
US20070199299A1 (en) * 2005-08-29 2007-08-30 Kashmerick Gerald E Combustion Engine
US20090022641A1 (en) * 2007-07-19 2009-01-22 Shau-Lin Franklin Chen Multilayered catalyst compositions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH653219A5 (de) * 1980-04-01 1985-12-31 Johnson Matthey Co Ltd Verfahren zur waermebehandlung von nahrungsmitteln.
JPS61145304A (ja) * 1984-12-17 1986-07-03 Ngk Insulators Ltd 複合サイクル発電方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857668A (en) * 1969-08-02 1974-12-31 Siemens Ag Flameless catalytic combustion of hydrocarbon in porous sintered stones
US3870455A (en) * 1973-12-10 1975-03-11 Engelhard Min & Chem Method for catalytically supported thermal combustion
US3928961A (en) * 1971-05-13 1975-12-30 Engelhard Min & Chem Catalytically-supported thermal combustion
US3966391A (en) * 1973-12-10 1976-06-29 Engelhard Minerals & Chemicals Corporation Method of combustion using high temperature stable catalysts
US4047877A (en) * 1976-07-26 1977-09-13 Engelhard Minerals & Chemicals Corporation Combustion method and apparatus
US4088435A (en) * 1973-12-10 1978-05-09 Engelhard Minerals & Chemicals Corporation Method for the combustion of carbonaceous fuels utilizing high temperature stable catalysts
US4154568A (en) * 1977-05-24 1979-05-15 Acurex Corporation Catalytic combustion process and apparatus

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1059005B (de) * 1955-02-09 1959-06-11 Sterling Drug Inc Verfahren und Vorrichtung zur UEberhitzung von Daempfen
FR2127465A5 (sv) * 1971-03-05 1972-10-13 Bourret Jean
US3969899A (en) * 1972-04-18 1976-07-20 Sadaharu Nakazawa Fuel burning apparatus and heat engine incorporating the same
FR2201705A5 (sv) * 1972-10-04 1974-04-26 Brulfert Andre

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857668A (en) * 1969-08-02 1974-12-31 Siemens Ag Flameless catalytic combustion of hydrocarbon in porous sintered stones
US3928961A (en) * 1971-05-13 1975-12-30 Engelhard Min & Chem Catalytically-supported thermal combustion
US3870455A (en) * 1973-12-10 1975-03-11 Engelhard Min & Chem Method for catalytically supported thermal combustion
US3966391A (en) * 1973-12-10 1976-06-29 Engelhard Minerals & Chemicals Corporation Method of combustion using high temperature stable catalysts
US4088435A (en) * 1973-12-10 1978-05-09 Engelhard Minerals & Chemicals Corporation Method for the combustion of carbonaceous fuels utilizing high temperature stable catalysts
US4047877A (en) * 1976-07-26 1977-09-13 Engelhard Minerals & Chemicals Corporation Combustion method and apparatus
US4154568A (en) * 1977-05-24 1979-05-15 Acurex Corporation Catalytic combustion process and apparatus

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4966001A (en) * 1987-10-23 1990-10-30 General Electric Company Multiple venturi tube gas fuel injector for catalytic combustor
US5248251A (en) * 1990-11-26 1993-09-28 Catalytica, Inc. Graded palladium-containing partial combustion catalyst and a process for using it
US5250489A (en) * 1990-11-26 1993-10-05 Catalytica, Inc. Catalyst structure having integral heat exchange
US5258349A (en) * 1990-11-26 1993-11-02 Catalytica, Inc. Graded palladium-containing partial combustion catalyst
US5259754A (en) * 1990-11-26 1993-11-09 Catalytica, Inc. Partial combustion catalyst of palladium on a zirconia support and a process for using it
US5405260A (en) * 1990-11-26 1995-04-11 Catalytica, Inc. Partial combustion catalyst of palladium on a zirconia support and a process for using it
US5511972A (en) * 1990-11-26 1996-04-30 Catalytica, Inc. Catalyst structure for use in a partial combustion process
US8115373B2 (en) 2005-07-06 2012-02-14 Rochester Institute Of Technology Self-regenerating particulate trap systems for emissions and methods thereof
US20070045101A1 (en) * 2005-07-06 2007-03-01 Rochester Institute Of Technology Self-regenerating particulate trap systems for emissions and methods thereof
US8991153B2 (en) 2005-07-06 2015-03-31 Rochester Institute Of Technology Self-regenerating particulate trap systems for emissions and methods thereof
US8581480B2 (en) 2005-07-06 2013-11-12 Rochester Institute Of Technology Self-regenerating particulate trap systems for emissions and methods thereof
US8580087B2 (en) 2005-07-06 2013-11-12 Rochester Institute Of Technology Self-regenerating particulate trap systems for emissions and methods thereof
US20070044478A1 (en) * 2005-08-29 2007-03-01 Kashmerick Gerald E Combustion engine
US7765785B2 (en) 2005-08-29 2010-08-03 Kashmerick Gerald E Combustion engine
US20070199299A1 (en) * 2005-08-29 2007-08-30 Kashmerick Gerald E Combustion Engine
US8007750B2 (en) * 2007-07-19 2011-08-30 Basf Corporation Multilayered catalyst compositions
US20090022641A1 (en) * 2007-07-19 2009-01-22 Shau-Lin Franklin Chen Multilayered catalyst compositions

Also Published As

Publication number Publication date
DE2918515A1 (de) 1979-11-15
SE7904004L (sv) 1979-11-09
JPS54164031A (en) 1979-12-27
CA1146362A (en) 1983-05-17
FR2425539A1 (fr) 1979-12-07
JPS5514991A (en) 1980-02-01

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